Preparation of 5, 8-dihydro-5, 8-methano-1, 4-naphthalenedisulfonamides



United. States. Patent 3,375,275" PREPARATION OF5,8-DIHYDRO-5,8METHAN0'- 1,4-NAPHTHA-IJENEDISULFONAMIDES-- Joseph E;Dunbar,- Midland;.Mich., assignor tolTheDow Chemical. Gompany, .Midland,.Micli., a; corporation; of

Delaware:

NoDrawing; Continuation-impart f application-:Ser.-.N0.a

, 366,150, May. 8,. 196.4,. This, application. June 26, 1964;.

The portion oftlie term of tlrepatent subsequenfto Jan." 30, 1979, g hasbeen disclaimed and dedicated to the Public' 1 Claim; (Cl; 2'60'-556)This application is a continuation-impart;ottmy pending application Ser.No; 36 6;150;.filedMay" 8;.1964, now US. Patent 3,268,581.

The present invention isdirected to a novel method of preparingmono-cyclopentadiene adducts of p-quinonedisulfonimides havingtheformula IIIHSOER is reacted with cyclopentadi'ene: The reaction iscarried out in the'pres'ence' ofa' tertiary amine'as a catalyst andpreferably in the presence of an inert organic solvent-as reactionmedium. Suitablesolvents include chloroform, carbon tetrachloride,benzene, toluene, methylene chloride and 'tetrachloroethane.- Thereaction proceeds: readily at temperatures between 0 and -l 10 C. and ispreferably carried out between 20 and IOO C'. The reactionmixture' ismaintained at the reaction temperaturefem: period of time to insurecompletionof th'ere'action.

The" amounts of the p-quinonedisulfonimideand 'cycloa pentadienereactants to be employed are notcritical, some of thedesired-product;beingeobtained when: em! ploying any amounts of said.starting materials. For the production of the desiredproducts, it-ise'ssential 'that the tertiary amine catalyst be; employed:-.in at.least: a; cata-z lytic amount. Large amounts of the catalyst can beemployed, such as molecular proportions of the catalyst equal to twicethe molecular proportions of the employed p-quinonedisulfonimide.However, the use of the catalyst in large amounts is not necessary noris it desirable from the standpoint of economy. Suitable catalystsinclude pyridine, lutidine, picoline, quinoline, trialkylamines andN,N-dialkyl=anilines such as trimethylamine, tributyl- ICC? amine,dipropylmonoethylamine, diethylpropylamine, N,

N-dimethylaniline, N,N-diamylaniline, N,N-dipropylaniline, N-,Ndiethylaniline= andso forth;- Preferred trialkylamines andN;N-dialkylanilines include those wherein lower alkylis employed torefer toalkyl containing firom 1 to carbon atoms, inclusive; Thereaction consumes.

thecyclopentadiene and p-quinonedisulfonimide compoundsin substantiallyequir'nolar proportionsand the use. of" these starting materials. in"such proportions ispre ferr'ed. In a'prefrred procedure; the oat'alystis employed atf a' concen'tration' of'one m-illimol of catalyst' forevery mole of cyclbpentadiene or p quinonedisulfonimide ern'- ployed inthe reaction:

In carrying' out the reaction; thep-quin0nedisulfoniinide,cyclopent-adiene and' tertiary amine can be combined in anyconvenientorder or. fashion. However, it is" preferred that" thereactants be dispersed in an organic l'iquida-s reaction medium. Thereaction proceeds rapidly with'the'conta'cting and mixingofthereactants. For optimum yields, thereaction' mixture is maintained at thereaction temperature for the period of' time to insure completion of thereaction.

-As.the;-reactionproceeds,. the naphthalene disulfona-mide product may;precipitate out. of'the reaction mixture. As the reaction nearscompletion there is observed a substantial cessation in theprecipitation of the desired product.

Upon completion of the reaction the desired product is separated byconventional procedures. Thus, the reaction mixture can be filtered toseparate the precipitated 7 product. In those instances-wherein'theproduct fails to precipitate during the course of the reaction, thereaction mixture can be cooled or concentrated by distillation underreduced pressure and thereafter cooled, if necessary,.to precipitate thedesired-prodnctwhichis then collected as: described. Thisisolidproductcanbe further. purified. by common procedures including. washing.or recrystallization from a common organic solvent.

' The.followingtexamplfes-v are merely illustrative and are not to;beaconstrued as limiting naphthalnedimethdnesulfonamide NHS'OzCH'a' Viifns'oioni Cyclopentadiene (20 milliliters; 16.1 grams; 0.244 mole)istaddedto: a v warm mixture of p-quinonedimethanesulfonimide (52.4grams; 0.200 mole) and t'riethylamine (1.7 milliliters) in 3 liters of"chloroform. Immediatelyupon. the addition of .thecyclopentadiene, thereaction mixture turnsdarh brown and thermixture boilsspontaneously"Thereaction mixture is allowed to stand at roomtemperature for 63fhours. Duringthis' time period the. 598-.dihydro-5,8methanoI,4-naphthalenedimethanesulfonamide product precipitates as awhite crystalline solid. This product is then collected on a filter,washed with chloroform and air dried. The dried product has a meltingpoint of 211-212 C. and has carbon, hydrogen and nitrogen contents of47.79 percent, 4.87 percent, and 8.35 percent, respectively, as comparedwith the theoretical contents of 47.54 percent, 4.91 percent, and 8.53percent.

Patente'dMar. 26,. 1968.

Example 2.5,8-dihydr-5,B-methzmo-I,4-nizphthalenedin-propanesulfonamideNHSOzCHzCHrCHa l CH2 p-Quinonedi-n-propanesulfonimide (318.10 grams; 1.0mole) is added with stirring to a warm mixture of cyclopentadiene (82milliliters; 67 grams; 1.0 mole) and N,N- dimethylaniline (0.116milliliters; 0.001 mole) in 4 liters of toluene. The reaction mixture ismaintained at a temperature of 100 C. for hours. Following the heatingperiod, the reaction mixture is fractionally distilled under reducedpressure and gradually increasing. temperatures to remove the lowboiling constituents. During the concentration procedure, the5,8-dihydro-5,-8-methano-1,4-naphthalenedi-n-propanesulfonamide(molecular weight 636.2) product precipitates as a crystalline solid.This solid product is collected, washed with benzene and air dried.

In similar procedures 5,8-dihydro-5,8-methano-1,4- naphthalene npropylsulfonamide (molecular weight 636.2) is prepared by reactingtogether cyclopentadiene and p-quinonedi-n-propanesulfonimide. In onepreparation, the reaction is carried out in the presence of a catalyticamount of lutidine as catalyst, while in another the preparation iscarried out in the presence of a catalytic amount of pyridine.

Example3.-5,8-dihydro-5,8-methan0-1,4-naphthalenediisopropanesulfonamide CH3NHSOaCH NHSOzO Picoline (3 milliliters) is added with stirring to p-quisulfonamide (molecular weight 664.2) by reacting to gether,cyclopentadiene and p-quinonediisobutanesulfonimide in the presence ofquinoline.

The compounds prepared by the method of the present invention are usefulas pesticides. For such uses the unmodified compounds can be used. Inother operations, the product is dispersed on an inert finely dividedsolid and employed as a dust. Such mixtures can also be dispersed inwater with or without the aid of a surface active agent, and theresulting aqueous suspension employed as sprays. In other procedures,the product is employed as an active constituent in solvent solutions,oil-in-water or water-in-oil emulsions or aqueous dispersions. Inrepresentative operations, aqueous compositions containing ten pounds of5,8- dihydro5,8methano 1,4 naphthalenedimethanesulfonamide per 100gallons of ultimate mixture give good kills of southern armyworm. Thecompounds prepared by the methods of the present invention are alsouseful as intercedure, the 5,8-dihydro-5,8-methane-l,4-naphthalenediisopropanesulfonamide (molecular weight 636.2) product precipitates as acrystalline solid. This solid is then collected, washed withtetrachloroethane and air dried.

The following compounds of the present invention can be prepared in asimilar fashion.

5,8-dihydro5,8-methano 1,4 naphthalenediethanesulfonamide (molecularweight 610.2) by reacting cyclopentadiene andp-quinonediethanesulfonimide in the presence of a mixture ofdipropylethylamine and tributylamine.

5,-8-dihydro-5,8-methano 1,4 napthalenedibutanesulfonamide (molecularweight 664.2) by reacting together cyclopentadiene andp-quinonedibutanesulfonimide in the presence of N,N-diamylaniline.5,8-dihydro 5,8 methano-1,4n-aphthalenediisobutanemediates in thepreparation of the pesticidal compounds disclosed in my patentapplication Serial No. 366,150 filed May 8, 1964, now US. Patent3,268,581.

What is claimed is: 1. The method of preparing a compound correspondingto the formula NHSOzR which comprises reacting cyclopentadiene with ap-quinonesulfonimide having the formula ll NSOaR wherein in the formulaeR represents an alkyl group containing up to and including 4 carbonatoms; said reaction being carried out in the presence of at least acatalytic amount of tertiary amine.

References Cited UNITED STATES PATENTS 3,019,259 1/1962 Dunbar 260-5562,993,060 7/1961 Dunbar 260--396 3,288,816 1'1/1966 Dunbalr 260-556OTHER REFERENCES JOHN D. RANDOLPH, Primary Examiner. WALTER A. MODANCE,Examiner. H. I. MOATZ, Assistant Examiner.

1. THE METHOD OF PREPARING A COMPOUND CORRESPONDING TO THE FORMULA